Process for the manufacture of metal complexes of isoindoline azines

ABSTRACT

The invention relates to a simplified process for the manufacture of 1:1 metal complexes of isoindoline azines of the formula ##STR1## wherein R is hydrogen, alkyl or aryl, Q contains an isocyclic or heterocyclic radical, acyl, carbamoyl or thiocarbamoyl, and Y is the radical of an active methylene group or aromatic amine, which comprises reacting a compound HQ or a hydrazone with an ortho ester or amidine in the presence of a metal donor at elevated temperature in a polar solvent. Pigments made by this process are lightfast and are useful in coloring plastics.

This is a division of application Ser. No. 242,005 filed on Mar. 9, 1981, now U.S. Pat. No. 4,385,174.

The present invention relates to a process for the manufacture of 1:1 metal complexes of isoindoline azines of the formula ##STR2## wherein the ring A can be still further substituted, R is a hydrogen atom, an alkyl or aryl group, and Q is a group of the formula ##STR3## wherein B is an isocyclic or heterocyclic radical and R₁ is a hydroxyl or mercapto group or a radical of the formula ##STR4## wherein E is a 5- or 6-membered heterocyclic ring which may be fused with benzene nuclei and which contains a nitrogen atom β-oriented to the C* atom, an acyl group, an unsubstituted or a substituted carbamoyl or thiocarbamoyl group, V is an acyl, cyano or nitro group or an unsubstituted or substituted carbamoyl or thiocarbamoyl group, T is a 5- or 6-membered heterocyclic ring which may be fused with benzene nuclei and which contains a nitrogen atom β-oriented to the NH group, or is a radical of the formula ##STR5## wherein Z₁ is an oxygen or a sulfer atom, n is 1 or 2, X₃ is an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical, or an amino group which is unsubstituted or substituted by an alkyl, cycloalkyl, aralkyl, aryl or heteroaryl radical, and Y is the radical of a compound containing active methylene groups or of an isocyclic or heterocyclic aromatic amine, which process comprises (a) condensing a compound of the formula

    H--Q

or a hydrazone of the formula ##STR6## with an ortho-carboxylic acid ester of the formula

    R--C(OR.sub.2).sub.3                                       ( 6)

wherein R is as defined above and R₂ is an alkyl, araklyl or aryl group, or with an amidine of the formula ##STR7## wherein R is as defined above, R₂ ' has the same meaning as R₂ or is hydrogen, or with the salt of the amidine of the formula (7) with an organic or inorganic salt, and (b) reacting the condensation product with a compound of the formula (5) or H--Q, in the presence of a metal donor, at elevated temperature and in a polar organic solvent. The isoindolinone azines of the formula (1) can be substituted in the benzene ring A by halogen atoms, for example 2 to 4 chloride atoms, 1 to 2 alkyl or alkoxy groups, each of 1 to 4 carbon atoms, a phenyl, phenoxy, nitro or benzoylamino group, or an alkanoylamino group of 2 to 6 carbon atoms. Preferably, however, the benzene ring A is unsubstituted.

Y is preferably a radical ═N--R" or a methine radical of the formula ##STR8## wherein R' is an alkoxycarbonyl, alkylcarbamoyl, carbamoyl, thiocarbamoyl or sulfamoyl group, a benzylcarbamoyl group, a phenylsulfamoyl or phenylsulfonyl group which is unsubstituted or substituted by halogen atoms or alkyl groups of 1 to 4 carbon atoms, but is especially a group of the formula ##STR9## wherein Z₁ is an oxygen or a sulfer atom, X₁ is a hydrogen, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group of 1 to 4 carbon atoms, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group of 2 to 6 carbon atoms, a phenoxy, benzoylamino, phenylcarbamoyl or phenylsulfamoyl or phenylazo group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X₂ is a hydrogen, chlorine or bromine atom, an alkyl or alkyoxy group of 1 to 4 carbon atoms, and W is O, S, or NH. R" is a radical of the formula (10).

R is e.g. a phenyl or naphthyl radical, but is preferably a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, especially the methyl group.

If Q is a radical of the formula (2), B is e.g. a phenylene or naphthylene radical, especially a 5- or 6-membered heterocyclic ring which may be fused with benzene nuclei and which contains a nitrogen, oxygen or sulfur atom β-oriented to the C* atom and which may contain a further nitrogen atom in the ring and a fused benzene ring and/or a further heterocyclic ring. R₁ is preferably a hydroxyl group. Preferred radicals of the formula (2) are: ##STR10## wherein W is O, S or NH, X₁ and X₂ have the meanings assigned to them above and R₄ is alkyl of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 6 carbon atoms or carbamoyl.

If Q is a radical of the formula ##STR11## wherein E and V are acyl groups, these groups are preferably acetyl or benzoyl groups. E and V as unsubstituted or substituted carbamoyl or thiocarbamoyl groups are preferably alkylcarbamoyl or alkylthiocarbamoyl groups containing 2 to 6 carbon atoms, benzylcarbamoyl groups, or groups of the formula (9).

E is a 5- or 6-membered heterocyclic ring which may be fused with benzene nuclei is preferably one containing a nitrogen atom β-oriented to the C* atom and N, O or S as further hetero-atom. Particularly interesting compounds are those of the formula (1), wherein Q is a radical of the formula ##STR12## wherein V₁ is an acetyl, cyano, benzoyl or carbamoyl group, an alkylcarbamoyl group containing 2 to 6 carbon atoms, a benzylcarbamyl group or a group of the formula ##STR13## wherein X₁ and X₂ have the given meanings, Z₁ is an oxygen or a sulfur atom and Z₂ is the group ##STR14## wherein X₁ and X₂ have the given meanings.

Formula (1) represents only one of the possible isomeric or tautomeric forms.

The starting hydrazones of the formula (5) are known compounds which can be obtained e.g. by the process described in British patent specification No. 1 467 595, by reacting an iminoisoindoline of the formula ##STR15## with hydrazine hydrate.

The compounds of the formula (16) are in turn obtained by condensing the corresponding 1-amino-3-iminoisoindolenine with an amine or with a compound containing active methylene groups, especially a compound of the formula

    NCCH.sub.2 R'                                              (17)

wherein R' has the above meaning.

Representative examples are those acetonitriles listed on page 7 of British patent 1 467 595, as well as cyanoaceto-o-chlorophenyl, -p-chlorophenyl, -m-chlorophenyl, -m-methylphenyl, -p-methylphenyl-, -3,4-dichlorophenyl-, -3,5-dimethylphenyl-, -3,4-dimethylphenyl, -3-chloro-4-methylphenyl-, -o-methoxyphenyl-, -2,4-dimethoxyphenyl-, -2,5-dimethoxyphenyl-, p-acetylamino-phenyl-, p-benzoylaminophenyl-, -3-chloro-4-methyl-, -p-chlorobenzoylaminophenyl-, -4-carbamoylphenyl-, -4-sulfamoylphenyl-, -4-phenylazophenyl-, -4-phenoxyphenyl-, -p-nitrophenyl-, -3-trifluormethylphenyl-, or -2-chloro-5-trifluoromethylphenylamides, 2-cyanomethyl-4-phenyl-, -4-p-nitrophenyl-, -4-fluorophenyl- or -4-methylphenylthiazole.

Suitable compounds containing active methylene groups are also heterocyclic compounds which contain an active methylene group in the heterocyclic ring, for example those listed in pages 7 and 8 of British patent specification No. 1 467 595, e.g. 2,4-dihydroxyquinoline, 1-p-chlorophenyl-3-methyl-5-pyrazolone, 1-p-methylphenyl-3-methyl-5-pyrazolone, 1-phenyl-3-dichlorovinyl-5-pyrazolone, 1-p-methylphenyl-3-dichlorovinyl-5-pyrazolone.

Examples of amines which donate the radical Y are aromatic, but especially heterocyclic, amines, preferably those in which the amino group is located directly at a 5- or 6-membered heterocyclic ring which can contain 1 to 3 nitrogen atoms and, in addition, oxygen and sulfur atoms. An unsubstituted or substituted benzene nucleus can be fused to the heterocyclic parent nucleus. Examples of such amines are those listed on pages 6 to 7 of British patent specification No. 1 467 595, and, in addition, 2-aminopyridine, diaminophthalazine, 2-amino-4-hydroxyquinoline, 2,6-diaminopyridine, 2-amino-4,5-dimethythiazole.

In the compound H--Q, Q is e.g. the radical of the formula (2), wherein R₁ is preferably a hydroxyl group and B is preferably a naphthalene radical or a 5- or 6-membered heterocyclic ring which contains an oxygen, a sulfur or, preferably, a nitrogen atom β-oriented to the C* atom and which may contain a further nitrogen atom in the ring and a fused benzene ring and/or a further heterocyclic ring.

Representative isocyclic hydroxy compounds are those of the formula ##STR16## wherein Y₂ is a hydrogen atom, a carboxyl or carbamoyl group, an alkoxycarbonyl or alkylcarbamoyl group containing 2 to 6 carbon atoms, a phenylcarbamoyl group which is unsubstituted or substituted in the phenyl moiety by halogen atoms or alkyl or alkoxy groups of 1 to 4 carbon atoms, and Y₃ is a hydrogen or halogen atom, or a methoxy, nitro or cyano group.

Examples of isocyclic hydroxy compounds are: 2-naphthol, 6-bromo-2-naphthol, 6-nitro-2-naphthol, 2,3-hydroxynaphthoic acid, 2-hydroxy-3-naphthoanilide, 2-hydroxy-6-bromo-3-naphthoanilide. Exemplary of a cycloaliphatic compound which contains active methylene groups is 5,5-dimethylcyclohexane-1,3-dione (Dimedon).

Heterocyclic hydroxy compounds are preferred, for example the compounds of the formula ##STR17## wherein X₁, X₂ and W have the above meanings, and those of the formula ##STR18## wherein R₆ is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, a phenyl or hydroxyl group, or those of the formula ##STR19## wherein X₁, X₂ and R₆ have the above meanings, and R₅ is a cyano group, an alkoxycarbonyl group of 2 to 6 carbon atoms or a carbamoyl group, or those of the formula ##STR20## wherein X₁ and X₂ have the given meanings, and, finally, pyrazoles

of the formula ##STR21## wherein R₄, X₁ and X₂ have the above meanings.

Representative examples are:

2,4-dihydroxyquinoline

2,4-dihydroxy-5,6,7 or 8-chloroquinoline

2,4-dihydroxy-6,8- or 7,8-dichloroquinoline

2,4-dihydroxy-6,7 or 8-methylquinoline

2,4-dihydroxy-6-chloro-8-methylquinoline

2-methyl-4-hydroxyquinoline

2-methyl-4-hydroxy-6-chloroquinoline

2-methyl-4-hydroxy-6-methoxyquinoline

3-hydroxyisoquinoline

barbituric acid

2-methyl-4,6-dihydroxypyrimidine

4-hydroxycoumarin

4-hydroxy-6-methylcoumarin

4-hydroxy-6-methoxycoumarin

4-hydroxy-6-chlorocoumarin

4-hydroxy-6-chloro-5,7-dimethylcoumarin

1-phenyl-3-methylpyrazol-5-one

1-phenyl-3-carboxypyrazol-5-one

1-phenyl-3-carbamoylpyrazol-5-one

1-phenyl-3-methoxycarbonylpyrazol-5-one

1-phenyl-3-ethoxycarbonylpyrazol-5-one

1-o-chlorophenyl-3-methylpyrazol-5-one

1-p-chlorophenyl-3-methylpyrazol-5-one

1-o-methylphenyl-3-methylpyrazol-5-one

1-p-methylphenyl-3-methylpyrazol-5-one.

Preferred compounds H--Q are the compounds of the formula ##STR22## and, in particular, those of the formula ##STR23## wherein V, V₁, E, Z₁ und Z₂ are as defined above.

Examples of compounds of the formula (26) are the substituted acetonitriles listed on page 7 of British Pat. No. 1 467 595, and also

acetoacetylaniline

acetoacetyl-p-chloroaniline

acetoacetyl-o-methoxyaniline

acetoacetyl-2,5-dimethoxy-4-chloroaniline

2-acetoacetylaminobenzimidazole

thiocarbamoylacetonitrile

N-phenylthiocarbamoylacetonitrile

N-p-chlorophenylthiocarbamoylacetonitrile

N-p-tolythiocarbamoylacetonitrile

N-p-acetylaminophenylthiocarbamoylacetonitrile

N-m-trifluoromethylphenylthiocarbamoylacetonitrile

N-p-phenoxyphenylthiocarbamoylacetonitrile

N-p-nitrophenylthiocarbamoylacetonitrile

N-α-naphthylthiocarbamoylacetonitrile

N-p-methoxyphenylthiocarbamoylacetonitrile

thioacetylacetone

thioacetoacetonilide

N-cyclohexylthiocarbamoylacetonitrile

cyanoacetamide

cyanoaceto-N-methylamide

cyanoaceto-p-chloroanilide

acetylacetophenone

cyanoacetophenone

2-cyanomethylbenzimidazole

2-cyanomethylquinazol-4-one.

If Q is the radical of the formula (4), H₂ NT can either ba a heterocyclic amine or a thiocarbamoyl derivative.

Preferred heterocyclic amines of the formula H₂ NT are those in which the amino group is located at a 5- or 6-membered heterocyclic ring which contains a nitrogen atom β-oriented to the amino group and may contain N, O or S as further hetero-atom and which can be fused through benzene rings. Representative heterocyclic amines are the amines listed on pages 6-7 of British Pat. No. 1 467 595, (or listed at column 5, line 63 to column 6, line 46 of the equivalent U.S. Pat. No. 4,022,770, which list is incorporated herein by reference) and also 3-aminoisoindolenin-1-one, 1-amino-4-chlorophthalazine or 1,4-diaminophthalazine and the imine forms thereof.

Preferred thiocarbamoyl derivatives of the formula H₂ NT are those in which T is the radical of the formula ##STR24## wherein Z₁ and n have the given meanings and X₃ is an amino group which is substituted by a heteroaryl or aryl radical of the formula ##STR25## wherein X₁ and X₂ have the given meanings.

As ortho-carboxylic acid esters of amidines of the formulae (6) and (7) it is preferred to use those in which R₂ is alkyl of 1 to 4 carbon atoms and R₂ ' is alkyl of 1 to 4 carbon atoms or phenyl.

As metal donors it is preferred to use the salts of zinc, cadmium, manganese, cobalt, iron, and especially of copper and nickel, and mixtures of such metals. It is preferred to use the formates, acetates or stearates of these metals.

The reaction of the components can be carried out in varying sequence. It is preferred to condense the hydrazone of the formula (5) with the ortho-carboxylic acid ester of the formula (6) or the amidine of the formula (7) to give the azine of the formula ##STR26## wherein Z is a group --OR₂ or --NHR₂ ', in which R₂ and R₂ ' have the given meanings, and to react the latter with the compound H--Q in the presence of the metal donor.

One variant of the process consists in condensing the compound H--Q with the ortho-carboxylic acid ester of the formula (6) or an amidine of the formula (7) in the presence of the metal donor, and reacting the condensation product with the hydrazone of the formula (5).

The reaction of the hydrazone (5) with the ortho-carboxylic acid ester is preferably carried out in an excess of this latter, and the other reactions are carried out in a polar organic solvent, especially a hydrophilic polar solvent, for example an amide such as dimethyl formamide, formamide, dimethyl acetamide or N-methylpyrrolidone, as well as dimethyl sulfoxide, acetonitrile or an alcohol, e.g. ethyl cellosolve. A mixture of polar solvents can also be used.

The reaction temperature is advantageously in the range from 100°-200° C. The metal complex is isolated in conventional manner by filtration. The filter cake is washed thoroughly with solvent. The product is obtained in excellent yield and purity and can be used, without further purification, in finely dispersed form for coloring organic material of high molecular weight, e.g. cellulose ethers and esters, such as ethyl cellulose, acetyl cellulose, nitrocellulose, polyamide and polyurethanes, or polyesters, natural resins or synthetic resins, e.g. aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylates, thermoplastics or curable acrylic resins, rubber, casein, silicone and silicone resins, singly or in mixtures. The specified materials of high molecular weight can be in the form of plastics, melts or of spinning solutions, lacquers, or printing inks. Depending on the end-use, it is advantageous to use the pigments of the present invention as toners or in the form of preparations.

The pigment can be used in the form in which it is obtained in the synthesis or in slightly ground form to give opaque colorations. However, it can also be more thoroughly ground to give transparent colorations, for example strong metal effect finishes.

Mill base formulations in lacquers have advantageous flow properties.

The colorations obtained e.g. in plastics, filaments and lacquers, have high colour strength, excellent purity of shade, good dispersibility, good fastness to overspraying, migration, heat, light and migration as well as good gloss.

The manufacture of 1:1 metal complexes of azines of the formula ##STR27## by condensing the corresponding hydrazono-isoindoline with an oxo compound of the formula ##STR28## and subsequent metalation, is described in British Pat. No. 1,467,595. Compared with this prior art process, the process of the present invention constitutes a simplified procedure.

The invention is illustrated by the following Examples, in which percentages are by weight.

EXAMPLE 1

(a) (11.6 g (0.06 mole) of 75% 1,3-diiminoisoindoline and 11.7 g (0.06 mole) of cyanoaceto-p-chloroanilide are dissolved in 50 ml of dimethyl formamide and 3.6 ml (0.06 mole) of glacial acetic acid and the solution is stirred overnight at room temperature. Complete reaction to 1-(cyano-p-chlorophenylcarbamoylmethylene)-3-iminoisoindoline is confirmed next day by thin-layer chromatography. Then 3.1 ml of hydrazone hydrate (0.06 mole) are added dropwise at room temperature and in the course of 1 to 2 minutes to the resultant suspension. The mixture is stirred at room temperature for 45 minutes. Subsequent analysis by thin-layer chromatography confirms that the 1-(cyano-p-chlorophenylcarbamoylmethylene)-3-iminoisoindoline is completely reacted. 250 ml of ethanol are then added to the mixture, which is thoroughly stirred at room temperature for 15-20 minutes. The precipitate is collected by filtration, washed with a small amount of ethanol and dried overnight in vacuo at 50°-60° C., affording 16.8 g (83% of theory) of the compound of the formula ##STR29## in the form of a yellowish brown powder.

(b) 1 drop of concentrated sulfuric acid is added to 25 ml of triethyl orthoformate and the mixture is heated to 140° C. With stirring, 3.4 g (0.01 mole) of the compound obtained in (a) are added in portions at the same temperature. The mixture is allowed to react for 1 hour at 140° C., while simultaneously distilling off alcohol. The mixture is then cooled to 80° C. and filtered. The filter cake is washed with alcohol and dried overnight in vacuo at 80° C., affording 3.54 g (90% of theory) of the compound of the formula ##STR30## in the form of an orange powder.

Microanalysis: C₂₀ H₁₆ N₅ O₂ Cl mol.wt. 393.83 Found: 61.00% C; 4.10% H; 17.79% N; 9.00% Cl. Calculated: 61.00% C; 4.3% H; 17.8% N; 9.0% Cl.

EXAMPLE 2

1 drop of conc. sulfuric acid is added to 40 ml of triethyl orthoacetate and the mixture is heated to 130°-135° C. Then 6.75 g (0.02 mole) of the compound obtained in Example 1(a) are added in portions at the same temperature in the course of 30 minutes. The reaction is allowed to go to completion for 1 hour at 140° C. and the mixture is then cooled to 80° C. and filtered. The filter cake is washed with alcohol and dried in vacuo at 80° C., affording 6.95 g (85% of theory) of the compound of the formula ##STR31## in the form of an orange powder.

Microanalysis: C₂₁ H₁₈ N₅ O₂ Cl mol.wt. 407.86 Calculated: 61.84% C; 4.45% H; 17.17% N; 8.69% Cl. Found: 61.4% C; 4.2% H; 17.8% N; 9.1% Cl.

In accordance with the procedure of Example 1 or 2, a hydrazone of the formula ##STR32## is reacted with an ortho-carboxylic acid ester of the formula

    R.sub.1 '--C(OR.sub.3 ").sub.3

to give compounds of the formula ##STR33## wherein Y', R₁ ' and R₃ " have the meanings given in Table 1.

                                      TABLE 1                                      __________________________________________________________________________     Example                                                                             Y'                            R.sub.1 '                                                                          R.sub.3 "                               __________________________________________________________________________           ##STR34##                    H   C.sub.2 H.sub.5                           4                                                                                  ##STR35##                    CH.sub.3                                                                           C.sub.2 H.sub.5                           5                                                                                  ##STR36##                    H   CH.sub.3                                  6                                                                                  ##STR37##                    H   CH.sub. 3                                 7                                                                                  ##STR38##                    H   C.sub.2 H.sub.5                           8                                                                                  ##STR39##                    CH.sub.3                                                                           C.sub.2 H.sub.5                           9                                                                                  ##STR40##                    CH.sub.3                                                                           CH.sub.3                                  10                                                                                 ##STR41##                    H   C.sub.2 H.sub.5                           11                                                                                 ##STR42##                    H   C.sub.2 H.sub.5                           12                                                                                 ##STR43##                    CH.sub.3                                                                           C.sub.2 H.sub.5                           13                                                                                 ##STR44##                    H   C.sub.2 H.sub.5                           14                                                                                 ##STR45##                    CH.sub.3                                                                           C.sub.2 H.sub.5                           15                                                                                 ##STR46##                    CH.sub.3                                                                           C.sub.2 H.sub.5                           16                                                                                 ##STR47##                    CH.sub.3                                                                           C.sub.2 H.sub.5                           17                                                                                 ##STR48##                    H   C.sub.2 H.sub.5                           18                                                                                 ##STR49##                    H   CH.sub.3                                  19                                                                                 ##STR50##                    H   C.sub.2 H.sub.5                           20                                                                                 ##STR51##                    H   C.sub.2 H.sub.5                           21                                                                                 ##STR52##                    H   C.sub.2 H.sub.5                           22                                                                                 ##STR53##                    H   C.sub.2 H.sub.5                           23                                                                                 ##STR54##                    H   C.sub.2 H.sub.5                           24                                                                                 ##STR55##                    H   C.sub.2 H.sub.5                           25                                                                                 ##STR56##                    H   C.sub.2 H.sub.5                           26                                                                                 ##STR57##                    H   C.sub.2 H.sub.5                           27                                                                                 ##STR58##                    H                                                                                   ##STR59##                                28                                                                                 ##STR60##                    H   C.sub.4 H.sub.9                           29                                                                                 ##STR61##                    H                                                                                   ##STR62##                              __________________________________________________________________________

EXAMPLE 30

(1.97 g (0.005 mole) of the compound obtained in Example 1(b) and 1.31 g (0.0052 mole) of nickel acetate tetrahydrate are suspended in 35 ml of dimethyl formamide and the mixture is heated to 60° C. Then 1.05 g (0.005 mole) of 1-p-chlorophenyl-3-methyl-5-pryazolone are added and the mixture is further heated to 115° C. The reaction is allowed to go to completion for 11/2 hours at the same temperature, then the mixture is cooled to 80° C. and filtered. The filter cake is washed with dimethyl formamide and alcohol and dried in vacuo at 80° C., affording 2.3 g (75% of theory) of the 1:1 nickel complex of the formula ##STR63##

Microanalysis: C₂₈ H₁₇ Cl₂ N₇ O₂ Ni mol.wt. 613.1 Calculated: 54.80% C; 2.77% H; 11.58% Cl; 15.98% N; 9.57% Ni. Found: 54.5% C; 2.9% H; 11.4% Cl; 16.2% N; 9.8% Ni.

The above metal complex pigment colors plastics in pure scarlet shades of excellent fastness properties.

EXAMPLE 31

The procedure of Example 30 is repeated using 5,5-dimethyl-1,3-cyclohexanedione instead of 1-p-chlorophenyl-3-methyl-5-pyrazolone. Working up gives a 1:1 nickel complex (65% of theory) of the formula ##STR64## R₁ '=H

Microanalysis: C₂₆ H₂₀ ClN₅ O₃ Ni mol.wt. 544.6 Calculated: 57.34% C; 3.7% H; 12.86% Cl; 6.5% N; 10.78% Ni. Found: 57.1% C; 3.8% H; 13.1% Cl; 6.4% N; 10.9% Ni.

This nickel complex colors plastics in pure orange shades of excellent fastness properties.

EXAMPLE 32

The procedure of Example 31 is repeated, using the compound obtained in Example 2 instead of that obtained in Example 1(b), to give also a pure orange metal complex of the formula of Example 31 (R₁ '=CH₃).

EXAMPLE 33

3.03 g (0.01 mole) of the compound of the formula ##STR65## (obtained from hydrazine hydrate and 1-(cyanophenylcarbamoylmethylene)-3-iminoisoindoline) are suspended in 40 ml of dimethyl formamide. Then 2 ml (0.012 mole) of triethyl orthoformate are added and the reaction mixture is heated to 80° C. and stirred for 10 minutes at the same temperature. A warm solution (80° C.) of 2.08 g (0.01 mole) of 1-p-chlorophenyl-3methyl-5-pyrazolone and 2.6 g (0.0105 mole) of nickel acetate tetrahydrate in 25 ml of dimethyl formamide is then added to the mixture, which is heated to 115° C. After a reaction time of 2-3 hours at the same temperature, the mixture is cooled to 80° C. and filtered. The filter cake is washed with dimethyl formamide and alcohol and dried overnight in vacuo at 80° C., affording 4.7 g (81% of theory) of the 1:1 nickel complex of the composition C₂₈ H₁₈ ClN₇ O₂ Ni and having the formula ##STR66##

Microanalysis: C₂₈ H₁₈ ClN₇ O₂ Ni mol.wt. 578.66 *Calculated: 57.9% C; 3.14% H; 16.9% N; 6.1% Cl; 10.1% Ni. Found: 57.4% C; 3.3% H; 17.0% N; 6.1% Cl; 10.4% Ni.

EXAMPLE 34

2.08 g (0.01 mole) of 1-p-chlorophenyl-3-methyl-5-pyrazolone are suspended in 40 ml of dimethyl formamide. After addition of 2 ml (0.012 mole) of triethyl orthoformate, the mixture is heated to 80° C. and stirred for 10 minutes at this temperature. Then 2.6 g (0.0105 mole) of nickel acetate tetrahydrate are added and stirring is continued for 5 minutes at 80° C. Then 3.03 g (0.01 mole) of the 1-(cyanophenylcarbamoylmethylene)-3-hydrazinoisoindoline of the formula ##STR67## are added and the reaction mixture is heated to 115° C. and stirred for 21/2 hours at this temperature, then cooled to 80° C. The pigment is isolated by filtration and dried overnight in vacuo at 80° C., affording 3.05 g (53% of theory) of a 1:1 nickel complex pigment which is identical with the product of Example 33.

EXAMPLES 35-49

Table 2 lists further nickel complexes of the formula ##STR68## (for simplicity's sake only one of the possible isomeric or tautomeric forms is indicated) which are obtained substantially in accordance with the procedure of Example 30 or 33 either by condensing the reaction mixture of a hydrazone of the formula ##STR69## with triethyl orthoformate or triethyl orthoacetate, or the azine of the formula ##STR70## in the presence of nickel acetate tetrahydrate, with a compound of the formula ##STR71## which contains active methylene groups, in which formulae Y', R, V and E have the meanings given in columns 2, 3, 4 and 5 respectively. Column 6 indicates the shade obtained in polyvinyl chloride.

                                      TABLE 2                                      __________________________________________________________________________                                                   Shade                            Example                                                                             Y'                          R V     E    in PVC                           __________________________________________________________________________     35                                                                                   ##STR72##                  H acetyl                                                                               phenyl- amino                                                                       red                                36                                                                                 ##STR73##                  H cyano p-chloro- phenyl- amino                                                             red                                37 "                           H p-methyl-                                                                            p-methyl-                                                                           red                                                                 phenyl-                                                                              phenyl-                                                                  carbamoyl                                                                            amino                                 38   "                           H acetyl                                                                               phenyl-                                                                             red                                                                       amino                                 39   "                           H 2-benz-                                                                              methyl                                                                              claret                                                              imida-                                                                         zolyl                                         40                                                                                 ##STR74##                  H cyano amino                                                                               orange                             41 "                           H cyano methyl-                                                                             orange                                                                    amino                                   42                                                                                 ##STR75##                  H cyano benzyl- amino                                                                       orange                             43                                                                                 ##STR76##                  H acetyl                                                                               phenyl                                                                              orange                             44                                                                                 ##STR77##                  H cyano phenyl                                                                              orange                           45   2-benzimidazolylimino       H cyano p-chloro-                                                                           orange                                                                    phenyl-                                                                        amino                                 46   2-benzthiazolylimino        H cyano p-chloro-                                                                           red                                                                       phenyl-                                                                        amino                                 47   2-benzoxazolylimino         H cyano p-chloro-                                                                           orange                                                                    phenyl-                                                                        amino                                   48                                                                                 ##STR78##                  H cyano phenyl- amino                                                                       red                                49                                                                                 ##STR79##                  H cyano phenyl- amino                                                                       red                              __________________________________________________________________________

EXAMPLE 50

2.36 g (0.006 mole) of the compound prepared in Example 1(b) and 1.57 g (0.0068 mole) of nickel acetate tetrahydrate are heated in 40 ml of N-methylpyrrolidone to about 80° C. Then 1.06 g (0.006 mole) of cyanoacetothioanilide are added and the reaction is allowed to go to completion for 11/2 hours at 145° C. The reaction mixture is then cooled to 80° C. and filtered. The filter cake is washed with dimethyl formamide and alcohol and dried overnight in vacuo at 80° C., affording 2.22 g (64% of theory) of a red 1:1 nickel complex of the formula ##STR80## which has excellent fastness properties.

Microanalysis: C₂₇ H₁₆ ClN₇ OSNi mol.wt. 580.7: Calculated: 55.85% C; 2.78% H; 16.88% N; 5.52% S; 6.11% Cl; 10.11% Ni. Found: 55.1% C; 3.1% H; 16.4% N; 5.5% S; 5.8% Cl; 9.6% Ni.

EXAMPLES 51-55

Table 3 lists further nickel complexes of the formula ##STR81## (only one of possible isomeric or tautomeric forms is indicated) which are obtained substantially in accordance with Example 30 or 33 by condensing the azine of the formula ##STR82## in the presence of nickel acetate tetrahydrate, with a heterocyclic compound of the formula ##STR83## which contains active methylene groups, in which formula Y", R, Z and ##STR84## have the meanings given in columns 2, 3, 4 and 5 respectively. The shade obtained in PVC is indicated in column 6.

                                      TABLE 3                                      __________________________________________________________________________      Example                                                                             Y"                   R                                                                                Z                                                                                         ##STR85##   in PVCShade                __________________________________________________________________________     51                                                                                   ##STR86##           H                                                                                 ##STR87##                                                                                 ##STR88##  red                           52 "                    H                                                                                 ##STR89## "           red                           53 "                    H OC.sub.2 H.sub.5                                                                           ##STR90##  yellow                        54 "                    H OC.sub.2 H.sub.5                                                                           ##STR91##  red                           55 "                    H OC.sub.2 H.sub.5                                                                           ##STR92##  violet                      __________________________________________________________________________

EXAMPLE 56

2.36 g (0.006 mole) of the compound obtained in Example 1(b) 1(b) and 1.57 g (0.0063 mole) of nickel acetate tetrahydrate are suspended in 40 ml of N-methylpyrrolidone. After addition of 0.94 g (0.006 mole) of benzimidazolylacetonitrile, the mixture is heated to 140° C. and stirred at the same temperature for 11/2 hours, then cooled to 50° C. and filtered. The filter cake is washed with dimethyl formamide and alcohol and dried at 80° C. in vacuo, affording 2.2 g (63% of theory) of a 1:1 nickel complex pigment of the formula ##STR93## which colors plastics in claret shades of excellent fastness properties.

Microanalysis: C₂₇ H₁₅ ClN₈ ONi mol.wt. 561.6 Calculated: 57.74% C; 2.69% H; 19.95% N; 6.31% Cl; 10.45% Ni. Found: 57.5% C; 3.0% H; 20.0% N; 6.1% Cl; 10.6% Ni.

EXAMPLE 57

1.97 g (0.005 mole) of the compound obtained in Example 1(b) and 1.31 g (0.00525 mole) of nickel acetate are suspended in 40 ml of N-methylpyrrolidone and the mixture is heated to 80° C. Then 0.73 g (0.005 mole) of 1-imino-3-isoindolinone are added and the reaction is allowed to go to completion for 11/2 hours at 145° C. The reaction mixture is then cooled to 80° C. and filtered. The filter cake is washed with dimethyl formamide and alcohol and dried overnight at 80° C. in vacuo, affording 1.62 g (63% of theory) of a 1:1 nickel complex of the formula ##STR94##

Microanalysis: C₂₆ H₁₄ ClN₇ O₂ Ni mol.wt. 515.16: Calculated: 56.72% C; 2.56% H; 17.81% N; 6.44% Cl; 10.66% Ni. Found: 56.0% C; 2.7% H; 17.5% N; 6.4% Cl; 10.9% Ni.

This complex colors plastics in pure scarlet shades of excellent fastness properties.

EXAMPLES 58-66

Table 4 lists further nickel complexes of the formula ##STR95## (for simplicity's sake only one of the possible isomeric or tautomeric forms is indicated) which are obtained in accordance with the procedure of Example 57 by condensing an azine of the formula ##STR96## in the presence of nickel acetate tetrahydrate, with an amine of the formula R'NH₂, in which formulae Y, R' and R have the meanings given in columns 2, 3 and 4 respectively. The shade obtained in polyvinyl chloride is indicated in column 6.

                  TABLE 4                                                          ______________________________________                                                                               Shade                                    Example                                                                               Y            R'NH.sub.2   R    in PVC                                   ______________________________________                                         58                                                                                     ##STR97##   1-amino-4-chloro- phthalazine                                                               H    red                                        59   "            2-amino-benz-                                                                               H    red                                                          imidazole                                                  60     "            2-amino-benz-                                                                               CH.sub.3                                                                            red                                                          imidazole                                                  61     "            3-amino-indazole                                                                            H    red                                      62     "            3-aminoiso-  H    red                                                          indoleninone                                                                   (3-imino-                                                                      isoindolinone)                                             63     "            2-amino-     CH.sub.3                                                                            red                                                          benzimidazole                                              64     "            1,4-diamino- H    orange                                                       phthalazine                                                65     2-benzthiazolyl-                                                                            3-amino-iso- H    orange                                          imino        indoleninone                                               66     2-benzimidazolyl-                                                                           2-amino-     H    orange                                          imino        benzimidazole                                              ______________________________________                                    

EXAMPLE 67

2.2 g (0.011 mole) of N,N'-diphenylformamidine and 3.4 g (0.01 mole) of the compound obtained in Example 1a) are suspended in 25 ml of dimethyl formamide. The mixture is heated to 135°-140° C. and stirred for 1 hour at the same temperature, then cooled to room temperature. After addition of 80 ml of alcohol the mixture is stirred thoroughly for 15 minutes at room temperature. The precipitate is collected by filtration, washed with a small amount of alcohol and dried overnight at 50°-60° C. in vacuo, affording 3.3 g (75% of theory) of the compound of the formula ##STR98## in the form of a yellow orange powder.

Microanalysis: C₂₄ H₁₇ N₆ OCl mol.wt. 440.5: Found: 65.6%; C 3.9% H 19.2%; N 7.9%; Cl. Calculated: 65.38%; C 3.85% H 19.06%; N 8.05% Cl.

EXAMPLE 68

The procedure of Example 67 is repeated, using N,N'-di-n-propylformamidine instead of N,N'-diphenylformamidine. Working up affords the compound of the formula ##STR99##

EXAMPLE 69

The procedure of Example 33 is repeated, using the corresponding amount of N,N'-dipropylformamidine instead of triethyl orthoformate. The same red 1:1 nickel complex is obtained as in Example 33.

EXAMPLE 70

1.25 g (0.005 mole) of nickel acetate tetrahydrate and 1.96 g (0.005 mole) of the compound obtained in Example (1b) are suspended in 40 ml of dimethyl formamide and the mixture is heated to 115°-120° C. After 5 minutes reaction time at this temperature the mixture is cooled to 40° C. and, after addition of 0.69 g (0.005 mole) of thiobenzamide, slowly heated to 100°-105° C. The reaction is allowed to go to completion for 1 hour at the same temperature, then the mixture is cooled to 70° C. and filtered. The filter cake is washed with dimethyl formamide and ethanol and dried overnight at 80° C. in vacuo, affording 1.7 g (61% of theory) of the compound of the formula ##STR100## in the form of a red powder.

Microanalysis: C₂₅ H₁₅ ClN₆ OSN mol.wt. 541.6: Calculated: 55.44% C; 2.79% H; 15.52% N; 5.92% S; 6.55% Cl; 10.84% Ni. Found: 55.4% C; 3.1% H; 16.0% N; 5.5% S; 6.7% Cl; 10.7% Ni.

This complex colors plastics and lacquers in red shades of excellent fastness properties.

EXAMPLES 71-83

Table 5 lists further nickel complexes of the formula ##STR101## (for simplicity's sake only one of the possible isomeric or tautomeric forms is indicated) which are obtained substantially in accordance with the procedure of Example 70 by condensing an azine of the formula ##STR102## in the presence of nickel acetate tetrahydrate, with a thiocarbamoyl derivative of the formula ##STR103## in which formulae Y, R and Z₃ have the meanings given in columns 2, 3, and 4 respectively. The shade obtained in polyvinyl chloride is indicated in column 5.

                  TABLE 5                                                          ______________________________________                                                                            Shade                                       Example                                                                               R       Z.sub.3             in PVC                                      ______________________________________                                         71     H                                                                                       ##STR104##         red                                           72   CH.sub.3                                                                               "                   red                                         73     H       CH.sub.3            yellow                                      74     H       NH.sub.2            claret                                        75   H                                                                                       ##STR105##         red                                           76   CH.sub.3                                                                               "                   claret                                        77   H                                                                                       ##STR106##         red                                           78   H                                                                                       ##STR107##         red                                           79   H                                                                                       ##STR108##         red                                           80   H                                                                                       ##STR109##         red                                           81   H                                                                                       ##STR110##         red                                           82   H                                                                                       ##STR111##         red                                           83   H                                                                                       ##STR112##         red                                         ______________________________________                                    

EXAMPLE 84

A laboratory kneader having a capacity of 250 parts by volume is charged with 25 parts of the pigment obtained in Example 30, 100 parts of finely ground sodium chloride and 30 parts of diacetone alcohol. The mixture is kneaded for 5 hours with cooling and then discharged into 4000 parts by volume of water. Sodium chloride and diacetone alcohol go into solution and the pigment precipitates. The suspension is filtered and the filter cake is washed thoroughly with water and dried in a vacuum drying cabinet at 80° C.

EXAMPLE 85

65 parts of stabilised polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 part of the pigment obtained in Example 84 are stirred together and then rolled for 7 minutes at 160° C. on a two-roll calender to produce an orange-red sheet of very good fastness to light and migration.

EXAMPLE 86

10 g of titanium dioxide and 2 g of the pigment obtained in Example 84 are ground for 48 hours in a ball mill with 88 g of a mixture of 26.4 g of coconut alkyd resin, 24 g of melamine/formaldehyde resin (50% solids content), 8.8 g of ethylene gylcol monomethyl ether and 28.8 g of xylene. The resultant lacquer is sprayed onto an aluminium sheet, predried for 30 minutes at room temperature, and then stoved for 30 minutes at 120° C. A red finish of very good fastness to overspraying, light and atmospheric influences is obtained.

EXAMPLE 87

4 parts of the finely dispersed pigment of Example 84 are stirred into 20 parts of solvent of the following composition: 50 parts of Solvesso 150 (mixture of aromatic hydrocarbons), 15 parts of butylacetate, 5 parts of Exkin II (ketoxime-based levelling agent), 25 parts of methyl isobutyl ketone, 5 parts of silicone oil (1% in Solvesso 150). After complete dispersion has been attained (in about 15-60 minutes, depending on the type of stirrer), the binders are added, namely 48.3 parts of Baycryl L 530 (acrylic resin; 51% in xylene/butanol 3:1) and 23.7 parts of Maprenal TTX (melamine resin; 55% in butanol). The batch is briefly homogenised and the resultant lacquer is then applied by conventional methods, such as spraying or dipping) or--particularly for the continuous coating of sheet metal--by the coil-coating method, and stoved (30 minutes at 130° C.). The red finishes obtained are distinguished by very good levelness, high gloss and excellent dispersion of the pigment, as well as by excellent fastness to atmospheric influences.

EXAMPLE 88

The procedure of Example 84 is repeated, except that 2.78 parts of Staybelite Resin (available from HERCULES) are added to the kneading stock. The resultant product is a pigment with a 10% resin content which can be more easily incorporated and having improved dispersibility. 

What is claimed is:
 1. A process for the manufacture of a1:1 metal complex of an azine of the formula ##STR113## wherein the ring A is unsubstituted or is substituted by two to four halogen atoms, by one or two alkyl of 1 to 4 carbon atoms, by one or two alkoxy of 1 to 4 carbon atoms, by phenyl, by phenoxy, by nitro, by benzoylamino, or by an alkanoylamino of 2 to 6 carbon atoms, Y is a radical of the formula ##STR114## wherein R' is an alkoxycarbonyl, alkylcarbamoyl, carbamoyl, thiocarbamoyl or sulfamoyl group, a benzylcarbamoyl group, a phenylsulfamoyl or phenylsulfonyl group which is unsubstituted or substituted by halogen atoms or alkyl groups of 1 to 4 carbon atoms, a group of the formula ##STR115## wherein Z₁ is an oxygen or a sulfur atom, X₁ is a hydrogen, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group of 1 to 4 carbon atoms, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group of 2 to 6 carbon atoms, a phenoxy, benzoylamino, phenylcarbamoyl or phenylsulfamoyl or phenylazo group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X₂ is a hydrogen, chlorine or bromine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, W is O, S, or NH, and R" is a radical of the formula (10), R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or naphthyl, Q is a group of formula (2) ##STR116## wherein R₁ is a hydroxyl or mercapto group and B is an isocyclic or heterocyclic radical selected from the group consisting of phenylene, naphthylene, a 5- or 6-membered heterocyclic ring which may be fused with a benzene nuclei and which contains a nitrogen, oxygen or sulfur atom β-oriented to the C* atom and which may contain a further nitrogen atom in the ring and a fused benzene ring or a further heterocyclic ring, which 5- or 6-membered heterocyclic ring is selected from the group consisting of 2,4-dihydroxyquinoline, 2,4-dihydroxy-5,6,7 or 8-chloroquinoline, 2,4-dihydroxy-6,8- or 7,8-dichloroquinoline, 2,4-dihydroxy-6,7 or 8-methylquinoline, 2,4-dihydroxy-6-chloro-8-methylquinoline, 2-methyl-4-hydroxyquinoline, 2-methyl-4-hydroxy-6-chloroquinoline, 2-methyl-4-hydroxy-6-methoxyquinoline, 3-hydroxyisoquinoline, barbituric acid, 2-methyl-4,6-dihydroxypyrimidine, 4-hydroxycoumarin, 4-hydroxy-6-methylcoumarin, 4-hydroxy-6-methoxycoumarin, 4-hydroxy-6-chlorocoumarin, 4-hydroxy-6-chloro-5,7-dimethylcoumarin, 1-phenyl-3-methylpyrazol-5-one, 1-phenyl-3-carboxypyrazol-5-one, 1-phenyl-3-carbamoylpyrazol-5-one, 1-phenyl-3-methoxycarbonylpyrazol-5-one, 1-phenyl-3-ethoxycarbonylpyrazol-5-one, 1-o-chlorophenyl-3-methylpyrazol-5-one, 1-p-chlorophenyl-3-methylpyrazol-5-one, 1-o-methylphenyl-3-methylpyrazol-5-one, and 1-p-methylphenyl-3-methylpyrazol-5-one,or Q is a radical of the formula ##STR117## wherein E is an acyl group, an unsubstituted or a substituted carbamoyl or thiocarbamoyl group, V is an acyl, cyano or nitro group or an unsubstituted or substituted carbamoyl or thiocarbamoyl group, T is the radical of a heteroaryl amine selected from the group consisting of 2-aminothiophene, 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-methylsulfonylthiazole, 2-amino-5-cyanothiazole, 2-amino-4-methyl-5-nitrothiazole, 2-amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-amino-4-(4'-chloro)-phenylthiazole, 2-amino-4-(4'-nitro)-phenylthiazole, 2-aminopyrazole, 3-amino-1-phenylpyrazole, 3-aminoindazole, 5-methylsulfonyl-2-aminothiazole, 5-benzoyl-2-aminothiazole, 2-aminoimidazole, 4,5-dicyano-2-aminoimidazole, 4,5-diphenyl-2-aminothiazole, 2-amino-3,4-thiadiazole, 2-amino-3,5-thiadiazole, 3-amino-1,2,4-triazole, 2-amino-3,4-oxadiazole, 3-aminopyridine, 2-aminopyridine-N-oxide, 2-amino-benzthiazole, 2-amino-6-chlorobenzthiazole, 2-amino-6-methyl-benzthiazole, 2-amino-6-methoxy-benzthiazole, 2-amino-6-chloro-4-nitrobenzthiazole, 2-amino-6-bromo-4-cyanobenzthiazole, 2-amino-6-cyano-4-methylbenzthiazole, 2-amino-6-methyl-4-nitrobenzthiazole, 2-amino-6-methoxy-4-nitrobenzthiazole, 2-amino-6-butoxy-4-chlorobenzthiazole, 2-amino-4-chloro-5-methoxy-benzthiazole, 2-amino-4-bromo-6-methoxybenzthiazole, 2-amino-4,6-dichlorobenzthiazole, 2-amino-4,6-dibromobenzthiazole, 2-amino-4-methyl-6-(trifluoromethyl)-benzthiazole, 2-amino-4-methyl-6-propionyl-benzthiazole, 2-amino-4-chloro-6-methylsulfonyl-benzthiazole, 3-amino-benzisothiazole, 3-amino-5-chloro-benzisothiazole, 2-amino-3-cyanotetrahydrobenzthiophene, 2-amino-benzimidazole, 2-amino-6-chlorobenzimidazole, 2-amino-6-bromo-benzimidazole, 2-amino-6-methyl-benzimidazole, 2-amino-6-methoxybenzimidazole, 2-amino-6-ethoxy-benzimidazole, 2-amino-6-methylsulfonyl-benzimidazole, 2-amino-6-acetylaminobenzimidazole, 3-amino-isoindoleninone-1, 1,4-diaminophthalazine and 1-amino-4-chlorophthalazine, as well as their imine forms, or T is a radical of the formula ##STR118## wherein Z₁ is an oxygen or a sulfur atom, n is 1 or 2, X₃ is an alkyl, cycloalkyl, aralkyl or aryl radical, or an amino group which is unsubstituted or substituted by an alkyl, cycloalkyl, aralkyl or aryl radical, and the metal is selected from the group consisting of zinc, cadmium, manganese, conbalt, iron, copper and nickel, which comprises condensing a hydrazone of the formula ##STR119## with an ortho ester of formula

    R--C(OR.sub.2).sub.3                                       ( 6)

where A, Y and R are defined above and R₂ is alkyl of 1 to 4 carbon atoms, benzyl or phenyl, then reacting the product of the condensation of the hydrazone of formula (5) and the ortho ester of formula (6) with a compound of formula

    H--Q

where Q is defined above, in the presence of a metal salt selected from the group consisting of the formates, acetates and stearates of zinc, cadmium, manganese, cobalt, iron, copper and nickel, at a temperature of 100°-200° C. in a polar organic solvent.
 2. A process according to claim 1, wherein the compound H--Q is a compound of the formula ##STR120## wherein W is O, S or NH, X₁ is a hydrogen, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group of 1 to 4 carbon atoms, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group of 2 to 6 carbon atoms, a phenoxy, benzoylamino, phenylcarbamoyl or phenylsulfamoyl or phenylazo group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X₂ is a hydrogen, chlorine or bromine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, and R₄ is an alkyl, alkoxycarbonyl or carbamoyl group.
 3. A process according to claim 1, wherein the compound H--Q is a compound of the formula ##STR121## wherein V₁ is an acetyl, cyano, benzoyl or carbamoyl group, an alkylcarbamoyl group containing 2 to 6 carbon atoms, a benzylcarbamoyl group or a group of the formula ##STR122## X₁ is a hydrogen, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group of 1 to 4 carbon atoms, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group of 2 to 6 carbon atoms, a phenoxy, benzoylamino, phenylcarbamoyl or phenylsulfamoyl or phenylazo group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, X₂ is a hydrogen, chlorine or bromine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms,Z₁ is an oxygen or a sulfur atom, Z₂ is a phenyl radical or the group ##STR123##
 4. A process according to claim 1, wherein the compound H--Q is an amine of the formula ##STR124## wherein W is an oxygen or a sulfur atom or the NH group,X₁ is a hydrogen, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group of 1 to 4 carbon atoms, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group of 2 to 6 carbon atoms, a phenoxy, benzoylamino, phenylcarbamoyl or phenylsulfamoyl or phenylazo group which is unsubstituted by chlorine or bromine atoms or methyl groups, and X₂ is a hydrogen, chlorine or bromine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms.
 5. A process according to claim 1, wherein the compound H--Q is a thiocarbamoyl derivative of the formula ##STR125## wherein n is 1 or 2, Z₁ is an oxygen or a sulfur atom and X₃ is an amino group which is unsubstituted or substituted by a group of the formula ##STR126## X₁ is a hydrogen, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group of 1 to 4 carbon atoms, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group of 2 to 6 carbon atoms, a phenoxy, benzoylamino, phenylcarbamoyl or phenylsulfamoyl or phenylazo group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X₂ is a hydrogen, chlorine or bromine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms.
 6. A process according to claim 1 where in the hydrazone of formula (5) ring A is unsubstituted and Y is a radical of the formula ##STR127## wherein R' is an alkoxycarbonyl, alkylcarbamoyl, carbamoyl, thiocarbamoyl or sulfamoyl group, a benzylcarbamoyl group, a phenylsulfamoyl or phenylsulfonyl group which is unsubstituted or substituted by halogen atoms or alky groups of 1 to 4 carbon atoms, or a group of the formula ##STR128## wherein Z₁ is an oxygen or a sulfur atom, X₁ is a hydrogen, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group of 1 to 4 carbon atoms, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group of 2 to 6 carbon atoms, a phenoxy, benzoylamino, phenylcarbamoyl or phenylsulfamoyl or phenylazo group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X₂ is a hydrogen, chlorine or bromine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, W is O, S, or NH, and R" is a radical of the formula (10).
 7. A process according to claim 1 where in the ortho ester of formula (6) R is hydrogen or methyl, and R₂ is alkyl of 1 to 4 carbon atoms.
 8. A process according to claim 1 wherein the metal salt is a nickel salt.
 9. A process according to claim 1 wherein the polar organic solvent is N,N-dimethylformamide or N-methylpyrrolidone. 